Copolymers and method for the preparation thereof



COPOLYlVIERS AND METHODFORTHE PREPARATION THEREOF .WilliamS. Barnhart, Cranford, and ElizabethShen Lo, Elizabeth, N.J., .assignors, by mesne assignments, to Minnesota Mining and Manufacturing Company, St. 'Paul, Minn., a corporation of Delaware :No Drawing. Application March 28, 1955 ..Serial No. 497,428

" BTClaims. (Cl. 260-835) I'I'his invention relates to copolymers formed by copolymerizing esters of perchlorofluorocarboxylic acids with ethylenically unsaturated comonomers.

The esters which are copolymerized with the ethylenically unsaturated comonomers in accordance with the present invention are unsaturated esters of perchlorafluorocarboxylic acids, and these esters may be prepared in a variety of ways, for example, by direct esterification' of a perchlorofluorocarboxylic acid or a .perchlorofluoro ...acid chloride with an unsaturated alcohol,,,such,as allyl,

crotyl, tiglyl alcohols, and the like. These alcohols may also be halogen substituted, if desired. The preparation of these and other esters useful in the process of the present of the present invention is disclosed'in copending application Serial No. 493,554; filed March" 10, '1955, now

Patent No. 2,856,388. The esters which are useful in the present invention are those prepared, accordingto the disclosures of" the aforementioned application, from-perchlorofluorocarboxylic acids or perchlorofluoro acid ch10 ethylene, ,vinylidene fluoride, vinylidene chloride, trifluorobutadienes, trifluoromethyl butadienes, trifluoromethyl styrenes, and the like or hydrocarbons, such as ethylene, propene, butadiene, styrene, andzthe likeror oxygen-containing compounds, such as vinyl isobutyl ether, methyl methacrylate, butyl acrylate, vinyl butyrate, vinyl acetate, and the like or nitrogen-containing compounds,-such as acrylonitrile, acrylamide, fluoroacrylonitrile, trifluoromethyl ,acrylonitrile, and the like.

,The ratio, of, the perchlorofluorocarboxylic acid ester or diester to the ethylenically unsaturated comonomer in the reaction mixture may be between about 3:97 to 95:15 parts by weight, respectively, preferably between 5:95 to 80:20 parts by weight, respectively, depending upon the reactants copolymerized and the characteristics desired in the copolymer product. The temperaturepf polymerization may be between 30 C. and +150 C., preferably between 20 C. and 60 C. 'Thetimeof reaction may be between about 1 and-120 hours-preferably between 20 and 100'hours. The pressure-in the polymerization vessel mayabe'from'O 'to 1000 :p.s.i.g. The copolymers preferably are prepare'd underautogenouspressure, i.e., 0 to 500 p.s.i.g.

A number of polymerization recipes may be used to produce the copolymers of the invention. One oftthe' recipes which .may be .used.,is .a water .suspension type catalyst system in which a redox catalyst is used which United States Patent 2,931,790 *Patented. Apr... 5, 1

ice

comprises an oxidant and a reductant. The oxidant is preferably an inorganic persulfate, such as potassium persulfate, sodium persulfate, or ammonium persulfate,

be. used in a quantity equivalent to 0.05 to 5.0 parts .by

weight per parts of'total comonomers presentand preferably is used in the range of 0.1 to 2 parts by weight per 100 parts of total comonomers present. 'Abutfer such as sodium tetraborate may also be used, if desired, together with the oxidant and the reductant. Also, about 0.01: to 1 part by weight per 100 parts of total comonov-mers-present of a variable valence, metal salt. maybe used, this salt preferably being an iron saltsuch as ferrous sulfate of ferrous nitrate, and serving as an activator. However, the reductant and the variable valence metal salt may be eliminated, if desired, and the comonomers may be polymerized in a water suspension system .which contains the oxidant only.

It isalso advantageous to add to the water suspension type catalyst system a dispersing or emulsifying agent,

examples of which are the salts, preferably the ammonium salt or potassiumsalts of polyfiuorocarboxylic acids or perchlorofluorocarboxylic acids. The ammonium salt or potassium salts of polyfluorocarboxylic acids and perchlorofiuorocarboxylic acids are generally present in: a quantity-between 0.5 and about 10 parts by weight 'per '100 parts of total comonomers present. The copolymerization is preferably conducted under mildly alkaline 1954, as being useful as dispersing agents in polymerization reactions.

The copolymerization reactions may also be effected in a mass or bulk polymerization system using an organic-peroxide promoter at -a temperature within the range of about -30 to +30 C. Of the organic peroxide promoters which may be used, halogen substituted acetyl peroxides, such as trichloroacetyl peroxide, are preferred. Exemplary of other peroxideswhich may be used'are trifluoroacetyl peroxide, chloroacetyl peroxide, .difluoroacetyl peroxide, and perfluoropropionylw peroxide.

Solution polymerization generally is not used to produce the copolymers of the present invention, since the esters of perchlorofluorocarboxylic acids used as monomers are insoluble in ordinary solvents.

The copolymers of the present invention are useful :as rubber substitutes, adhesives, and laminates. The copolymers in this invention may be pressed at tempera- "turesbetween 300 to 350 F. to give continuous flexible films. These copolymers may also be molded at similar EXAMPLE 1 v, A number of copolymers of unsaturated esters and diesters of perchlorofluorocarboxylic acids were prepared.

The conditions for the preparation of these copolymers are listed in the tables below. The copolymers were prepared according to the following general method:

A glass polymerization tube was evacuated, flushed 1. r 7 T 2,931,790 a 4 siurn persulfate dissolved in about 50 grams of water. The pH of the solution was adjusted to 7 with potassium hydroxide solution.

The total quantity of water in each of the above recipes with nitrogen, and one of the following polymerization 5 is 200 grams. recipes was added thereto: The tube was then frozen in liquid nitrogen and the (1) 1 gram of potassium persulfate dissolved in 200 monomers were added separately in the quantities noted grams of water. in the tables below. The tube was frozen after each (2) 0.75 gram of perfluorooctanoic acid dissolved in addition and sealed under vacuum, after which it was 7 150 grams of water and 1 gram of potassium persulfate 10 placed in a constant temperature bath and tumbled enddissolved in 50 grams of water; The pH of the combined over-end at the temperature indicated and for the time emulsion medium was adjusted to 7 using a 2.5 percent specified in the tables below. The tube was then resolution of potassium hydroxide. frozen and the copolymers were removed and washed (3) In this recipe, the ingredients are separately added with hot water to remove emulsifying agents, inorganic .to the polymerization tube: 0.4 gram sodium metabi- 15 salts, and unreacted monomers. The copolymers were sulfite dissolved in 20 grams of water, 5 grams of potasthen dried in a vacuum oven at a temperature of 35 C. j sinm stearate dissolved in about v100 grams of water, the until constant weight was obtained, and an analysis for .pH of this solution being adjusted to 11 with potassium fluorine or chlorine was then made. hydroxide solution, andl. gram of potassium persulfate It will be obvious to those skilled in the art that many dissolved in about 80 grams of water. 20 modifications may be made within the scope of the pres- (4) 0.75 gram of Cl(CF -C FCl) CF COOH disent invention without departing from the spirit thereof, solved in about 150 grams of water and 1 gram of potasand the invention includes all such modifications.

Table I PRINCIPAL MONOMER: CKCF1CFGDaCF1COnCH1CH=OH1 Mole Ratio Principal Monomer/(1:) Weight Ratio Polymerization Conditions Charged Percent No. Comonomers (2:) Principal Conver- Appearance Charged Combined Monomer/.1: Time Temp., Recipe sion rs) C.

013:01 22. 4/77.6 27.51725; 50/50 90 50 (1) 92 Hard particles. CF2=CFCL 22.4/77.6 50/50 96 50 (2) 85 Transparent hard rub- Bl. CF =CFCL 22.4/77.6 50/50 24 50 (1) 68 Transparent slow rub- El. 4 CFFOFOI 10/90 47/53 29. 6/70.4 22 50 (1) 2s Trgmsparent sticky rub- 8!. 5 CFr=CFCl /90 29. 5/70.4 23 50 (1) 74 Wh'te owder. 6 CF =CFCL. 10/90 29. 5170.4 23 50 (4) s1 Doi 7 CF=CFC1-- 22. 4 775 50/50 29 50 1) 79 Hard rubber. s CFa= GFC1 224/776 50/50 23 50 (4) 77 Do.

homopolymer). CH=CFCH=CH- 20/80 275/725 58. 8/41.2 22 50 (1) 28 Short rubber. CH =CFCl 20/80 19.5/80.5. 46.8/53.2 22 50 (1) 78 Trarsjparent, resinous r11 er. CF1=CFCH=CH1. 20/80 48.6/5L4 22 50 1) 47 White short rubber. CH1=CClCH=CH2 15/85 44.6/55.4 72 25 1 Rubber. 13..- OF CHCF=CH;/ 21/79 50/50 24 50 (1) 18 Snappy rubber.

CF: V 14 CH =(7CH=OH 23/77 49.6/50.4 25 (1) 8 Transparent soft rubber.

i 15. oni=ccn=orn 23/77 1/09 49.0 504 '21 50 2 51 Rubber.

a V 1e.--" 0HF 10H=cm 10/90 2.5/97.5 ass/53.2 as 55 (9 64 Tough rubber.

17.. CF2=CFCH=CH2- 20/80 5.5/945 48.2/5L8 68 '65 2 52 Sh a bh 1s CFQ=CHCF=CH,- 20/80 3 4s.2 51.s as 65 isi 43 so ru b beri 19--- CHFCFCH=CHZ--. 10/90 BSA/61.6 68 e5 (2) 48 Short rubber.

Reason for unexpected analytical results undetermined.

. Table ll 5 PRINCIPAL MONOMER: CL(CFQCFCL)3OFQCO1CH2CH=CH1 Mole Ratio Principal Monomer/(z) Weight Rati Polymerization Conditions No Comonomers (z) l i ii l gercent A I I clpa ODVGI- W06 Charged Combined Monomer/.1: Time Temp., Recipe sion pp (grams) (hrs.) C.

1 om=orc1 201st) 53.11/45. 2 5s 5o (1) 45 we s 2...--. o1 c1=on, 20 s0 452 518 as 50 (1) so sort iubber.

Table 111 PRINCIPAL MONOMER: CH|=CHCH00C(CFgCFCLhCOOCHiCH IEH;

- MoleTRa'tlo Principal Monomer/(z) Weight Ratio Polymerization Conditions No Gomonorners (z) I, i ii l Cement A ,:r 1' cipa OHVGT- 63131106 Charged Combined Monomer/z Time Temp., Recipe sion pp (grams) (hrs.) C.

CF: CH7=(JCH=CH:.-.-... 10/90 /95 3212/6728 25 50 3 76 Soft rubber.

or =cro1-- .24 so 4 ss Wh't a F=0F01-- :24 60 4 9a D OP er cF,=cF01. 24 so 4 94 Do.

CF! 1 a 0H,= cH=- cm 51 49 as as a 90 Soft rubber.

8..-." CH ==CFCH=CH:. 7 44/56 68 65 7.2 71 Short rubber. 1--- or, =c1ac1 crr, ems/cs2 as 65 s as Very short rubben. 8....-. CFg CFCH=CH:.- 34.8/65.2 68 '66 2 77 Rubbery hardpartieles.

Reason for unexpected analytical resultsundetermined.

We claim: 8. Aicopolymersof between about 3 :and about 97 .parts and about 97 1. A-copolymer of between about 3 parts by weight of a perchlorofluorocarboxylic acid ester of a carbon-to-carbon unsaturated alcohol and between about'95 and'about15 parts by weightof a polymerizable ethylenically unsaturated comonomer, said perchloro- 'fluorocarboxylic:acidcontaining recurring groups of j C cFc1 ZLA copolymer of between about 3 and about 97 :parts by 'weight of a -perchlorofluorocarboxylic acid monoesteriofw a. carbon-to-carbonunsaturated alcohol and 3. A copolymer of between'about 3 and about 97 parts by weight of a perchloroiluorocarboxylic acid diester of a carbon-to-carbon unsaturated alcohol and between about" 95 and about parts by-weight of a polymerizable zethylenically .unsaturated comonomer, said perchloroflu- :orocarboxylic acid containing recurring groups of '4. Acopolymer of between about 3 and about 97 parts "byweight ofa perchlorofiuoro carboxylic acid ester of 'a carbon-towarbon unsaturated alcohol and between about 95 and about 15 parts by weight of a polymerizable :ethylene .comonomer selected from the group consisting "offe'thyleneflnd halogenated hylenes, said Perchlorme:

carbon to=carbon unsaturatedtaloohol and between about 95 and about 15 parts by-weight of apolymerizable diene comonomer, said perchlorofluorocarboxylic acid contain- '6. Acoptilymer of between about 3 and about :97 parts by weight of a compound; having the formula .cinwhich n is an integer from 2 to 10 and R isan alkyenyl ;.--group,aandbetween; about 95 and about 15 parts by weight of aipolymerizable ethylenically unsaturated co- 1 monomer.

' 7. A copolymer of between about3 and about 97 parts by weight of a compound havingthe formula j -=i1l- WhiChn is an integer from 2 to 10 and R is analkenyl group, and between about 95 and about, 15' parts by weight of a polymerizableethylenically unsaturated comonomer.

by weight of a compound having the formula t 'o1(oF,--oFc1)..-1oF2c-'0-R in which'n is'an' integer from'Z to'10=and R isan alkenyl group; having -not in excess of about carbon atoms, "and between about 95 and about 15 parts by weightvof a polymerizable ethylenically unsaturated comonomer having not in excess of about 20 carbon atoms.

9.- A-co'polymer of between about 3 and about 97 parts by weight of acompound having the formula 7 R0- Gt(OFz-OFCl)n-zCtOR in whichn'is an integer from 2 to 10,and R is an' alkenyl 'tgroup'having not sin excess of abou-t 20 carbon atoms, and between about 95 and about 15 parts by weightjof 5 0a polymerizable ethylenically unsaturated comonomer having-not in: excess of about 20 carbon atoms.

10. A copolymer of between about 3 and about 97 parts by weight of a compound having the formula Ii 01(cFrCF0l),.-10Fr00- -R in which n is anflinteger from 2=to 10 and R is an alkenyl group having not in excess of about 20 carbon atoms; and between about 95 and about 15 parts by weight 'of' a polymeriiable ethylene comonomer.

11. A copolymer of between about 3 and about 97 parts by weight of-a compound having the formula ll i cK a-eCFQ Merge-0+1:

in Which); is an integer-from 2 to 10 and R isan alkeuyl grouphavingnot inexcess of about 20 carbon atoms, and between about and about 15 parts by weight-of. a polyrn'erizable 1diene I comonomer.

12. -A'-copolyrner of between about '3 and about 97 parts by weight of, a compound having the formula I O VR0 (0F-0F01)n-l 0rt '85 in which n isan integer from'2 to 10 and R is an alkenyl :group= hav.ing not-in excess of about 20 carbon atoms, and between about 95 and about 15 parts by weight of a polymerizable ethylene comonomer.

l3.'-Accopolymerof between about 3 and aboutv97 '70 parts by weight of a compound having the formula H II Ii R-O--C (CF CFCl)n-'1C--0R "in'which' nisaminteger from 2 to 10 and R. is analkenyl "(5 group having not in excess of about 20 carbon atoms",

aaamso and between about 95 and about 15 parts by weight of a polymerizable diene comonomer.

.14..A copolymer of between about 3 and, about 97 parts by weight of a compound having the formula -"in which n is an integer from 2 to 10 and R is an alkenyl group having not in excess of about 20 carbon atoms, and

between about 95 and about 15 parts by weight of chloro- 10 trifluoroethylene.

15. A copolymer of between about 3 and about 97 parts by weight of a compound having the formula 1 CI(CF CFCI),.-iCFz( J-O-R in which n is an integer from 2 to and R is an alkenyl;

"group having not in excess of about 20 carbon atoms,and "between about 95 and about parts by weight of 1- chloro, l-fluoroethylene.

16. A copolymer of between about 3 and about 97 parts by weight of a compound having the formula in which n is an integer from 2 to 10 and Ris an alkenyl group having not in excess of about carbon atoms. and between about 95 and about 15 parts by weight of fluoroprene. 3 17. A copolymer of between about 3 and about 97 parts by weight of a compound having the formula parts by weight of a compound having the formula in which n is an integer from 2 to 10 and R is an alkenyl' group having not in excess of about 20 carbon atoms, and between about 95 and about 15 parts by weight of 1,1,3- trifiuorobutadiene.

19. A copolymer of between about 3 and about 97 parts by weight of a compound having the formula in which n is an integer from 2 to 10 and R is an alkenyl group having not in excess of about 20 carbon atoms, and between about and about 15 parts by weight of chlorotrifluoroethylene.

20. A copolymer of between about 3 and about 97 21. A copolymer of between about 3 and about 97 parts by weight of a compound having the formula and between about 95 and about 15 parts by weight of chlorotrifluoroethylene.

22. A copolymer of between about 3 and about 97 parts by weight of a compound having the formula Cl(CFg-CFC1);OFa O-CH:CH=CHg and between about 95 and about 15 parts by weight; of chlorotrifiuoroethylene.

23. A copolymer of between about 3 and about 97 parts by weight of a compound having the formula V onom-oromorib-mom-orkcm and between about 95 and about 15 parts by weight of l-chloro, l-fluoroethylene.

24. A copolymer of between about 3 and about 97 parts by weight of a compound having the formula and between about 95 and about 15 parts by weight of chlorotrifiuoroethylene.

25. A copolymer of between about 3 and about 97 parts by weight of a compound having the formula CHaCHCHr-O (CF:-CFCl)s( !O-CHz-CH=CH1 and between about 95 and about 15 parts by weight of trifluoromethylbutadiene.

26. A process which comprises copolymerizing between about 3 and about 97 parts by weight of a per- 0 chlorofiuorocarboxylic acid ester of a carbon-to-carbon unsaturated alcohol and between about'95 and about 15 parts by weight of a polymerizable ethylenically unsaturated comonomer, at a temperature between about 30 C. and about C., said perchlorofiuorocarboxylic acid containing recurring groups of -CF CFCl--.

27. A process which comprises copolymerizing between about 3 and about 97 parts by weight of a compound having the formula Y in which n is an integer from 2 to 10 and R is an alkenyl group having not in excess of about 20 carbon atoms, and between about 95 and about 15 parts by weight of a polymerizable ethylenically unsaturated cornonomer having not in excess of about 20 carbon atoms, the process being carried out at a temperature of between about 30 C. and about +150 C.

28. A process which comprises copolymerizing between about 3 and about 97 parts by weight of a compound having the formula and between about 95 and about 15 parts by weight of chlorotrifluoroethylene at a temperature range of between about 30 C. and about +l50 C.

29. A process which comprises copolymerizing be- Parts by weight of a compound having the formula tween about 3 and about 97 p rts by welghtof a compound having the formula 01 0F,-cFc1),cF,ii-0cH,-oH=oH, and between about 95 and about 15 parts by weightof 5 chlorotrifluoroethylene at a temperature range of between about -30 C. and about +l50 C.

30. A process which comprises copolymerizing between about 3 and about 97 parts by weight of a compound having the formula and between about 95 and about 15 parts by weigh't of 31. A process which comprises copolymerizing between about 3 and about 97 parts by weight of a compound having the formula and between about 95 and about 15 parts by weight of trifluoromethylbutadiene at a temperature range of between about -30 C. and about +150 C.

References Cited in the file of this patent UNITED STATES PATENTS Coflrnan et a1. Dec. 14, Roedel Oct. 11, Cass Oct. 3, Kropa et a1 Jan. 30, Reid 2 Apr. 8, Miller Feb. 2, Coover et a1. Aug. 21,

UNITED STATES PATENT OFF ICE CERTIFICATE OF 'CORRECTIQN Patent No, 2,931,790 April 5, 1960 William S, Barnhant et al0 It is hereby certified that error appears in the-printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 5, lines 23, 31, 38, 45, 53, 59, and 68, column 6, lines 22, 32, 42, 51, 60, and 69, column 7, lines 3, 12, 22, 31, 40, 50, 59, and 68, column 8, lines 1, 8, 15,- 22, 30, 37, 50, 59, and 68, and column 9, lines 2 and 10, for "97", each occur rence, read 95 -g; column 5, lines 26, 34, 41, 48, 56, 65, and 73, column 6, lines 29, 39, 49, 58, and 67, column Z, lines 1, 1O, 2O, 29, 38, 48, 57, 66, and 74, column 8, lines 5, 13, 2O, 26, 32, 45, 55, 64, and 73, column 9, line 6, and column 10, line 1, for "95'", each occurrence, read 9T Signed and sealed this 8th day of November 1960a (SEAL) Attest:

KARL HQ AXLINE ROBERT C. WATSON Attesting Officer Commissioner of Patents 

1. A COPOLYMER OF BETWEEN ABOUT 3 AND ABOUT 97 PARTS BY WEIGHT OF A PERCHLOROFLUOROCARBOXYLIC ACID ESTER OF A CARBON-TO-CARBON UNSATURATED ALCOHOL AND BETWEEN ABOUT 95 AND ABOUT 15 PARTS BY WEIGHT OF A POLYMERIZABLE ETHYLENICALLY UNSATURATED COMONOMER, SAID PERCHLOROFLUOROCARBOXYLIC ACID CONTAINING RECURRING GROUPS OF 